MTRL 358: Hydrometallurgy I

Faculty of Applied Sciences Course Notes – Chapter IV:

Department of Materials Engineering Introduction to Leaching

1. Introduction

Leaching is the dissolution of solid materials into solution, invariably an

aqueous solution in hydrometallurgy. The solids are usually natural minerals, but also
include intermediate products of a process. Since we are always after one or a few
components, leaching should, ideally, be highly selective for the desired
mineral(s)/material(s). In practice we usually achieve partial selectivity, and, we
never completely dissolve the whole ore or feed material.

Leaching is virtually ubiquitous in hydrometallurgy and is often the key step

upon which the rest of the process hinges. Much has been written about the subject.
A key to understanding leaching is that it is an interfacial phenomenon; we are
utilizing heterogeneous chemical reactions. We are concerned with the solid-solution
interface, but also the gas-solution interface, whenever gaseous reactants (e.g. O2 g)
or products are involved. Thermodynamics, kinetics, transport phenomena, inorganic
reaction chemistry and other knowledge are involved.

This material provides an introduction to the topic. Underlying aspects of the

chemistry required to develop a flowsheet will be presented. This is followed by an
overview of leaching processes. Leaching may involve "co-current" and "counter-
current" flows of solids and solutions. This will be presented. A brief overview of
factors associated with agitation in leaching will be given. In a separate set of notes,
kinetic models for leaching will be developed.

The desired mineral(s)/material(s) need to be soluble in the chemical solution

to be used, and under practicable conditions:

• Practicable conditions have three aspects. The first is technical feasibility.

So, for instance, reactions rates need to be reasonably fast. Otherwise
excessively large equipment will be needed to allow suitably long enough
retention times. Reactions need to proceed to a high degree of completion
(high equilibrium constants), or else little conversion will be achieved.
Materials of construction for tanks, pipes, etc., need to be compatible with
the chemicals and conditions. There are many such considerations.

• The second aspect of practicable conditions is economic. Ideally we want to

use cheap reagents that will work with inexpensive materials, and so on. A
technically feasible process that is not cost effective will not succeed.
Together, these two factors greatly limit the number of available processes.

• The third aspect has to do with legislative and societal issues. For instance,
it is becoming increasingly difficult to build gold plants that use cyanide, due
to some recent environmental tragedies and public perceptions.

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 MTRL 358: Hydrometallurgy I
Faculty of Applied Sciences Course Notes – Chapter IV:
Department of Materials Engineering Introduction to Leaching

2. Leaching and Process Chemistry

This is the overarching chemical consideration for all hydrometallurgy

processes. And it is usually leaching that determines the chemical reaction medium
for the overall process. First consider the thermodynamic possibilities. This is often
done with the aid of Eh-pH diagrams and associated basic chemistry.

2.1 General Classes of Leaching Reactions

There are four possible things we can do to try to leach something in

hydrometallurgy:

• Dissolve in water
• Dissolve in acid or base (adjust pH)
• Oxidize or reduce it
• Form complexes with suitable ligands (complexants)

Combinations of these may be necessary. The more that has to be done, the greater
the complexity, and the higher the cost. The possibilities are outlined in the figure
below.

• Soluble in water. Leaching in hydrometallurgy involves water by definition.

If a mineral is readily soluble in water, e.g. CuSO4·5H2O (calcanthite), then
that is all that is needed. This is rare.

• Soluble in acid. Some minerals require only acid to dissolve.

• Soluble in base. Some minerals dissolve in basic solution, e.g. NaOH. Some
may be soluble in either acid or base; they are amphoteric. In general base
is more expensive than acid.

• Can be oxidized. Where a mineral cannot be readily dissolved in acid or base

alone, oxidation may be possible.

• Can be reduced. Few minerals can be treated in this way. Reducing agents
are more costly than oxidants, in general.

• The mineral can be dissolved by forming a complex, usually in acidic or basic

solution.

• A combination a complexant and an oxidant in acid or base, or much less

likely, complexant and reductant in acid or base may be needed.

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 MTRL 358: Hydrometallurgy I
Faculty of Applied Sciences Course Notes – Chapter IV:
Department of Materials Engineering Introduction to Leaching

OH-/Red/L?

H+/Red/L?
Increasing 4
OH-/Ox/L?
complexity
and/or cost
H+/Ox/L?
3
OH-/L? H+/L? Water? H+? OH-?
1
H+/Ox?

2 H+/Red?
H+ = acid
OH- = base
Ox = oxidant OH-/Ox?
Red = reductant
L = complexant OH-/Red?

Figure 1. Outline of chemical conditions that can be considered for leaching. The
diagram probably does not cover every single possible type of reaction, but most
hydrometallurgical leaching processes are included.

2.2 Illustrations of How to Choose a Leaching Medium

First consider the nature of the materials to be leached. Based on the solubility
rules for salts, most oxides, hydroxides and sulfides are insoluble in
water. This is important, because many of the minerals of interest are oxides,
hydroxides or sulfides. For any other mineral classes the same types of considerations
apply. Native metals (e.g. Au, Cu) are insoluble in water; they dissolve only by
corrosion. Some examples of how suitable leaching chemistry can be worked out from
basic principles are provided below.

Leaching of CuO and CuS

Based on the Ksp values for mineral compounds, many oxides and hydroxides
are soluble in acid at low, but practically attainable pH. Consider, for example,
dissolution of CuO in acid:

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 MTRL 358: Hydrometallurgy I
Faculty of Applied Sciences Course Notes – Chapter IV:
Department of Materials Engineering Introduction to Leaching

CuO s + H2O l = Cu+2aq + 2OH-aq Ksp = 2.2 x 10-21 (1)

2OH-aq + 2H+aq = 2H2O l K = (1/Kw)2 = 1 x 1028 (2)

CuO s + 2H+aq = Cu+2aq + H2O l Kl = Ksp/Kw2 = 2.2 x 107 (3)

The overall reaction is very favourable and CuO can be readily dissolved in acid
solution. This is confirmed by considering the CuO/Cu+2 vertical line in the Eh-pH
diagram for the Cu-H2O system shown in Figure 2.

0.8

Cu+2
0.6
O2
CuO
H2O
0.4
Eh volts

0.2

0 Cu Cu2O
H+
H2
-0.2

-0.4
0 2 4 6 8 10 12 14
pH
Figure 2. Eh-pH diagram for the Cu-H2O system with ionic activities set at 0.01 m,
and at 25°C.

The next question is how soluble is CuO at a given pH? This can be readily
determined from the equilibrium constant expression:

[Cu +2 ]
K= [1]
[H + ]2

log[Cu +2 ] = logK l − 2pH [2]

(The expression is readily derived from the expression for pH of a vertical line used
to draw Eh-pH diagrams.) In this example, at pH 3.67 the solubility of Cu+2 will be
around 1 M (actually, the activity will be 1 M, and since such solutions are highly non-
ideal, the solubility will be less than this). Obviously the lower Kl, the less soluble the

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 MTRL 358: Hydrometallurgy I
Faculty of Applied Sciences Course Notes – Chapter IV:
Department of Materials Engineering Introduction to Leaching

mineral is at a given pH. Note that the slope of the log solubility vs. pH plot depends
on the moles H+/mol metal ion dissolved according to the chemical reaction. What
drives such reactions is the strong favourability for formation of water.

We did not pay attention to Cu2O, which appears in the Eh-pH diagram. Since
it lies below CuO, it would form only if we were to reduce a Cu(II) species (either
Cu+2 or CuO). If we leach in the open air, the presence of oxygen ensures that we
maintain a high enough potential (NB E°O2/H2O = 1.23 V) that reducing conditions do
not arise. (On the other hand, if for some reason we were to see Cu2O forming, it
would be telling us that some adventitious species present in the system was
generating a reducing environment.)

In general, sulfides are less soluble in water than oxides/hydroxides, and, H2S
is a much less favourable product after reaction with acid. Mostly, in such cases we
need to be able to oxidize the sulfide portion of the mineral, either to elemental sulfur,
or some other higher oxidation state form (usually sulfate). Consider the
Eh-pH diagram for the Cu-S-H2O system in Figure 3. From this diagram, it is clear

0.8
HSO 4 - SO 4 2-

0.6
Cu+2

0.4 CuO O2/H2O

Eh Volts

0.2
CuS Cu2S Cu2O
0
H+/H

-0.2 Cu2S
Cu
Cu HS -
H2S
-0.4
0 2 4 6 8 10 12 14
pH

Figure 3. The Cu-S-H2O Eh-pH diagram with ionic activities set to 0.01 m at 25°C.

that the only possibility for leaching CuS is in acid solution and with the use of an
oxidant. Oxygen is suitable oxidant, based on the fact that the O2/H2O reduction
potential (Eh) is greater than that required to sustain Cu+2 in solution over the whole

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 MTRL 358: Hydrometallurgy I
Faculty of Applied Sciences Course Notes – Chapter IV:
Department of Materials Engineering Introduction to Leaching

of the region where Cu+2 is stable. And these considerations are verified by the
following reactions:

CuS s = Cu+2aq + S2-aq Ksp = 8 x 10-37 (4)

CuS s + 2H+aq = Cu+2aq + H2S g Kl = 1.1 x 10-15 (5)

CuS s + 2O2 g = Cu+2aq + SO42-aq Kl' = 4 x 10109 (!) (6)

To this point thermodynamics is serving us accurately. Only oxidation in acid

solution can be used to leach CuS. But now we come up against the discrepancy
between thermodynamics and kinetics that is rather common in hydrometallurgy; for
instance, oxygen alone reacts very slowly, particularly near room temperature with
many minerals, including with CuS. However, bacteria of the family thiobacillus occur
naturally and are part of the earth's natural sulfur cycle. They can be readily adapted
for use in leaching, and they quite efficiently promote oxidation of several copper
sulfide minerals (and others). They oxidize the sulfide right through to sulfate,
forming sulfuric acid in the process. Thus bioleaching, as it is called, is commonly
practiced for some copper sulfide minerals in low grade ores (especially those from
which a concentrate cannot be readily made; if a concentrate can be made
pyrometallurgical methods are more likely to be employed).

Continuing with this theme, ferric ion is often used as a "surrogate" oxidant to
help overcome the inherent slowness of O2 as an oxidant:

Fe+3aq + e- = Fe+2aq E° = 0.77 V; ~0.68 V in aq. H2SO4 (7)

Ferric ions are often available in the ore from oxidation of pyrite, i.e. FeS2, or other
iron minerals. Ferric ion can oxidize many sulfide minerals (e.g. CuS) to form
elemental sulfur and aqueous Mn+ cation (e.g. Cu+2). In addition, a strain of bacteria
named thiobacillus ferrooxidans readily catalyzes oxygen oxidation of ferrous ion to
ferric. This is used to regenerate ferric ion. Then the ferric/ferrous couple is used as
a redox catalyst in the oxidative leaching process. To summarize:

CuS s + 2Fe+3aq = Cu+2aq + 2Fe+2aq + S s (8)

2Fe+2aq + 1/2O2 g + 2H+aq = 2Fe+3aq + H2O l (9)

(By thiobacillus ferrooxidans)

S s + 3/2O2 g + H2O l = H2SO4 aq (10)

(By thiobacillus thiooxidans and ferrooxidans)

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 MTRL 358: Hydrometallurgy I
Faculty of Applied Sciences Course Notes – Chapter IV:
Department of Materials Engineering Introduction to Leaching

Ferric ion is also used as a surrogate oxidant to catalyze O2 oxidation of metal

sulfides at higher temperature and pressures, such as in an autoclave. A good
example is sphalerite concentrate leaching (ZnS), which is practiced using autoclaves
at ~150°C and under oxygen pressure. Ferric ion catalyzes the O2 oxidation process,
which would otherwise be too slow, even under autoclave conditions. However, now
due to the higher temperature, ferrous can be readily reoxidized to ferric by oxygen.
(Bacteria do not survive under autoclave conditions.) The same applies to many
copper sulfides, but to date the economics of autoclave leaching have not been
favourable.

Considering the Eh-pH diagram for the Cu-S-H2O system alone might be
confusing. As far as thermodynamics is concerned, ferric ion is sufficiently strongly
oxidizing to convert CuS into Cu+2 and HSO4-, say at pH ~1. Yet when we react Fe+3
with CuS at ~25°C, we find that CuS does leach, but that Cu+2 and solid sulfur, S,
are formed, and not HSO4- (in the absence of sulfur-oxidizing bacteria). Nothing on
the diagram suggests that this would occur. Nor do we see that Cu2S forms. In fact,
if we start with Cu2S the first thing that happens is,

Cu2S s + 2Fe+3aq = Cu+2aq + 2Fe+2aq + CuS s (11)

It is imperative that we understand what the Eh-pH diagram is, and is not telling us.
In general thermodynamics tells us what is possible; that a reaction may or may not
be spontaneous (occur naturally, on its own, without energy input), or that if it is not
spontaneous, what we have to do to make it go (input some form of energy). What
it does not tell us is the intermediate steps or reactions that may be involved in
getting from some initial state (e.g. CuS + ferric sulfate at pH 1 and 25°C) to some
final state (such as Cu+2aq, HSO4-aq, Fe+2aq, pH 1, 25°C). That is the domain of kinetics.
Thermodynamics does not care if it takes a millisecond or a million years. In the limit
of long enough time, it simply tells us what will occur. An Eh-pH diagram is even
more constrained. It tells us what the most stable state is for some combination of
elements (for our purposes in water) under specified conditions of pH and
electrochemical potential*, e.g. Cu, S and H2O. What it does
__________________________________________________________________
*And how do we maintain some specified set of conditions? Acids or bases are used to
adjust pH; a redox couple can be used to maintain an electrochemical potential (likewise an
electrical power supply attached to an electrochemical cell). The pH control seems easy
enough, but the latter works in much the same way. Recall the Nernst equation, as illustrated
below for the Fe+3/Fe+2 couple:

2.303RT a
E = E° - log Fe+2
F aFe+3

An electrochemical potential can be maintained somewhere near E° (about 0.68 V in sulfuric

acid solution) by maintaining a fixed ratio of ferrous:ferric ion activities. Now, note the
similarity to the equation for the pH of a weak acid:

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 MTRL 358: Hydrometallurgy I
Faculty of Applied Sciences Course Notes – Chapter IV:
Department of Materials Engineering Introduction to Leaching

a A-
pH = pK a + log
aHA

where A- and HA are a conjugate acid base pair. Substantial and similar concentrations of an
oxidant and its corresponding reductant (a redox couple) may act as an electrochemical
potential buffer, just as an acid and its conjugate base can act as a pH buffer (controlling the
pH near pKa). The additional complexity in the case of electrochemical potential is that for a
given reaction and set of conditions, many redox couples react very slowly, while others react
rapidly. Those that react rapidly do establish, or bring into effect the electrochemical potential
that thermodynamics says they will. Those that react slowly do not do so in a practical period
of time; kinetics inhibits. Knowing which situation pertains is a matter of experience, though
there are good chemical reasons. It is more common (though not universally so) that acids
and bases react quite rapidly to establish the expected pH.

not tell us is that there are numerous other possible half reactions and thus chemical
reactions. Some of the possibilities are qualitatively summarized in the figure below.
The two reduction half reaction couples indicated in bold correspond to lines on the
Eh-pH diagram in Figure 3. The other Cu/S reduction half reaction couples do not
appear on the diagram; neither does the Fe+3/Fe+2 couple. The Eh for each couple
would be the value for some specified pH < 2, where HSO4- is the dominant S(VI)
species. Double-headed arrows at right indicate the ∆E (cell potential) for ferric
oxidation of Cu/S species. (The Fe+2/Fe+3 activity ratio would have some specified
value, the exact value of which is not important here. What matters here is that
EhFe+3/Fe+2 lies above the other couples in the diagram.) From

Fe+3/Fe+2 0.68

Cu+2, S/CuS 0.56

Eh V

Cu+2, CuS/Cu2S 0.46

Cu+2, HSO4-/Cu2S 0.35

Cu+2, HSO4-/CuS 0.32
Cu2S, HSO4-/CuS 0.28
HSO4-/S 0.24

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 MTRL 358: Hydrometallurgy I
Faculty of Applied Sciences Course Notes – Chapter IV:
Department of Materials Engineering Introduction to Leaching

Figure 4. Half reaction potentials for a number of copper and/or sulfur species at
pH 1, 0.01 m ionic activities and 25°C (indicated by horizontal lines and the principal
oxidized/reduced species). The double-headed arrows indicate the potential
difference between Fe+3/Fe+2 (ferric acting as the oxidant; aFe+2/aFe+3 = 1) and some
of the copper/sulfur compounds couples (as reducing agents), e.g. Cu+2, HSO4-/Cu2S
corresponds to: 2Cu+2 + HSO4- + 7H+ + 8e- = Cu2S + 4H2O. Bold Cu/S couples at
left are depicted on the Cu-S-H2O diagram in Figure 3.

this diagram and the Eh-pH diagram we can see that Fe+3 is a strong enough oxidant
to be able to spontaneously oxidize CuS into Cu2S and Cu2S into Cu+2 and HSO4-.
These two half reactions represent the boundaries between the CuS/Cu2S and
Cu2S/Cu+2, HSO4- regions, respectively. And since these are the thermodynamically
most stable species for the relevant Eh-pH domains, they are the only ones depicted
on the Eh-pH diagram. But, as we have already noted, ferric oxidations of CuS to
Cu2S + HSO4- and of Cu2S to Cu+2 + HSO4- are exceedingly slow. Likewise, the
thermodynamically favourable oxidation of CuS to Cu+2 and HSO4- (as suggested by
the Eh-pH diagram) by Fe+3 occurs only exceedingly slowly. Although other half
reactions depicted in Figure 4 do not appear as boundaries between regions on the
Eh-pH diagram, they are otherwise perfectly valid half reactions. Thus Cu2S can be
oxidized by Fe+3 to CuS and Cu+2, and CuS can be oxidized to Cu+2 and S; the cell
voltages (e.g. ∆E = EFe+3/Fe+2 - EhCu+2, CuS/Cu2S =
0.68 - 0.46 = 0.22 V) are positive, and therefore the reactions are favourable. Finally,
note that while the oxidation of S to HSO4- by Fe+3 is quite favourable, this reaction
is exceedingly slow. Thus an Eh-pH diagram, while a good place to start, does not
provide any information about kinetics, and kinetics may obviate some favourable
transformations, even perhaps the most favourable ones. Then other reactions may
actually occur in practice, and these will still be thermodynamically favourable, even
if not the most favourable.

Finally, note too then that an Eh-pH diagram provides no certain information
on the steps through which a reaction can occur. Looking at the Cu-S-H2O diagram
we might naively expect that ferric leaching of CuS would first from Cu2S, then Cu+2
+ HSO4-. In fact this does not occur.

Gold Leaching

Gold occurs in nature as the element (more commonly as an alloy of Au and

Ag, or Au and Te, etc.). Ores may contain as little as 1-10 g Au/t (only 1-10 parts
per million!). Gold metal is insoluble in water, regardless of pH. Can it be oxidized?
There are two common oxidation states. Au(I) and Au(III). The simple cations Au+
and Au+3 are both powerfully oxidizing:

Au+aq + e- = Au s E° = 1.69 V (7)

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 MTRL 358: Hydrometallurgy I
Faculty of Applied Sciences Course Notes – Chapter IV:
Department of Materials Engineering Introduction to Leaching

Au+3aq + 3e- = Au s E° = 1.41 V (8)

Compare this with the stability of water:

O2 g + 4H+aq + 4e- = 2H2O l E° = 1.23 V (9)

Even in strongly acidic solution (aH+ = 1 m) either cation is thermodynamically able

to oxidize water to form O2. An Eh-pH diagram for the Au-H2O system would show
only one species within the bounds of stability of water at all pH - Au metal. What
about the kinetics? After all, some powerful oxidizing agents can be dissolved in water
even though thermodynamics says they should oxidize it to O2. Two examples are
cerric sulfate, i.e., Ce(IV) in sulfuric acid solution (E° = 1.44 V) and KMnO4 (E° =
1.51 V). However, experience confirms that both Au+ and Au+3 are rapidly reduced
by water at all pH. Leaching gold by simple oxidation is not an option.

There are no known stable uncharged complexes of Au so complexation alone

is not an option either. This leaves only the possibilities of routes 4 in
Figure 1. There are a number of known Au(I) complexes, including [Au(CN)2]-,
[Au(S2O3)2]3-, [Au(SC(NH2))2]+, etc. and some Au(III) complexes, e.g. [AuCl4]-. The
most stable is [Au(CN)2]-. An Eh-pH diagram for the Au-H2O-CN system is shown in
Figure 5. The gold-cyanide complex is seen to be exceedingly stable. The complex
can be formed by reaction between gold metal, cyanide and oxygen from air:

2Au s + 4CN-aq + O2 g + 2H2O l = 2[Au(CN)2]- + H2O2 aq + 2OH-aq (10)

(Hydrogen peroxide, H2O2, is a strong oxidant and will react with various species in
solution, being reduced to OH- in the end.) The process was patented in 1887 and is
the basis for much of the world's gold industry today. This leaching reaction is always
carried out in a basic solution. However, the cyanide complex is stable even in acid
solution. So why not run the process in acid (which is cheaper than base)? First, the
reaction is slow in acid. But, more importantly, CN- is a weak base:

HCN aq = H+aq + CN-aq Ka = 5.25 x 10-10; pKa = 9.28 (11)

In acid solution, the reverse reaction is very favourable (1/Ka = 1.91 x 109).
Furthermore, the vapour pressure for HCN over an aqueous solution is significant:

HCN aq = HCN g K = 0.1 (12)

And, finally, HCN is very toxic. In the end basic conditions are a must. The pH required
for effective leaching and occupational safety is around 10.5-11. Lime is able to
sustain this pH easily, so it is used rather than the more costly NaOH.

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 MTRL 358: Hydrometallurgy I
Faculty of Applied Sciences Course Notes – Chapter IV:
Department of Materials Engineering Introduction to Leaching

2.0
Au(OH)3 s
1.5
O2

1.0 H2O
Eh volts

0.5 [Au(CN)2]
-

H+
0.0
H2

-0.5 Au s
HCN aq CN-
-1.0
0 2 4 6 8 10 12 14
pH
Figure 5. Eh-pH diagram for the Au-H2O-CN system, 25°C, 1 x 10-5 m ionic activity
for [Au(CN)2]- (~10 mg/L Au) and 0.01 m for CN- and HCN.
However, cyanide leaching is not without problems. Sodium cyanide is a very
expensive reagent ($1000-2000 per tonne). One of the main issues in cyanide
leaching for Au is excessive reagent consumption. Many metal ions form very stable
cyanide complexes (e.g. [Cu(CN)3]-, [Zn(CN)4]2-, [Fe(CN)6]4-, etc.); CN- is fairly
easy to oxidize, forming OCN- in some cases; SCN- is readily formed by reactions of
some metal sulfides with cyanide. Many copper-gold mineral deposits with modest
concentrations of some copper minerals cannot be economically produced due to
excessive cyanide consumption. Finally, cyanide has a bad reputation and obtaining
permits to open a new gold cyanidation plant may be very difficult in several
jurisdictions.

The Eh-pH diagram for the Au-H2O-Cl system is shown in Figure 6. The
complexing species (NaCl and HCl for pH adjustment) are relatively inexpensive. Au
can be leached by a suitable oxidant in HCl solution, but, a rather high potential is
needed (close to 1 V; lower as aCl- increases) plus a high chloride concentration. This
presents a number of problems. O2 will work in principle, but it is slow in practice.
Other strong oxidants will tend to be expensive. Consumption of the oxidant may be
high for an ore consisting of sulfide minerals (which are fairly easy to oxidize), or
other oxidizable constituents (and steel). Further, AuCl4- is a strong oxidant, so even
mildly reducing materials in the ore will likely re-precipitate Au metal, defeating the
purpose. The strong chloride solutions are quite corrosive toward steel, so materials

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 MTRL 358: Hydrometallurgy I
Faculty of Applied Sciences Course Notes – Chapter IV:
Department of Materials Engineering Introduction to Leaching

of construction problems pertain. It is not hard to see why this type of chemistry is
not well suited for gold leaching in general.

1.5
-
AuCl4
Au(OH)3 s
1.0
Eh volts

O2
0.5
Au s H2O

H+
0.0
H2
0.1 m Cl-

1 m Cl-
-0.5
0 2 4 6 8 10 12 14
pH
Figure 6. Eh-pH diagram for the Au-H2O-Cl system, 25°C, 1 x 10-5 m activity for Au-
ions and 0.1 m (solid line) or 1 m (dashed line) for Cl-.

Bauxite Leaching

Bauxite is a mixture of aluminum oxide-hydroxide minerals. The principal

components are Al(OH)3, Al(O)OH and Al2O3·H2O. The final product of processing is
Al2O3. Bauxite ores contain the equivalent of 40-60% Al2O3. The solubility of the
minerals increases in the order: Al2O3 < Al(O)OH < Al(OH)3·H2O; the latter two are
the most commonly treated minerals. Both Al(O)OH and Al(OH)3 are soluble in
strongly acidic and strongly basic solutions; the compounds are amphoteric (both
weak acids and weak bases).

In basic solution:

Al(OH)3 s + OH- = [Al(OH)4]-aq (13)

Al(O)OH s + H2O l + OH-aq = [Al(OH)4]-aq (14)

0.5Al2O3 s + 1.5H2O l + OH-aq = [Al(OH)4]-aq (15)

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 MTRL 358: Hydrometallurgy I
Faculty of Applied Sciences Course Notes – Chapter IV:
Department of Materials Engineering Introduction to Leaching

In acid solution:

Al(OH)3 s + 3H+aq = Al+3aq + 3H2O l (16)

Al(O)OH s + 3H+aq = Al+3aq + 2H2O l (17)

0.5Al2O3 s + 3H+aq = Al+3aq + 1.5H2O l (18)

Aqueous Al+3 is present as [Al(H2O)6]+3 at very low pH, and as various OH-/H2O
complexes (hydrolyzed) as pH increases. The minimum solubility occurs at pH ~7.
Either strong base (NaOH) or strong acid is needed (e.g. H2SO4 or HCl) to attain the
necessary high or low pH, respectively. Solubility is significantly enhanced by
increasing temperature, and base or acid concentration. This is illustrated in
Figure 7. Here the equilibrium concentration of dissolved gibbsite, i.e. Al(OH)3, is
plotted as a function of temperature for various concentrations of NaOH. Note that
the solubility is expressed as Al2O3 in g/L, since that is the final product of the Bayer
process; 1 g Al(OH)3 = 0.6536 g Al2O3.

In fact, the Bayer process (patented in 1887) uses the strong base route at
elevated temperatures (autocalves). One might expect that H2SO4 or HCl would be
used since NaOH is so much more expensive. There are a number of reasons why
acid leaching is not used. A few of the key rationales are provided here.

1. Ferric-bearing minerals are much more soluble in acid solution than in basic
solution. Then a leach solution purification step for iron removal would be
needed. Ferric ion, Fe+3, is chemically similar in some respects to Al+3 and
removing ferric iron is prohibitively expensive.

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 MTRL 358: Hydrometallurgy I
Faculty of Applied Sciences Course Notes – Chapter IV:
Department of Materials Engineering Introduction to Leaching

Numbers on
200 curves indicate
[NaOH], g/L

150
Al2O3 g/L

100

50

10

30 70 110 150
Temperature °C
Figure 7. Equilibrium solubility of Al(OH)3 (expressed in terms of the equivalent mass
of Al2O3) in aqueous NaOH solutions as a function of temperature. (Adapted from:
L.K. Hudson, Critical Reports on Applied Chemistry, 1987, 20 pp. 11-46.)

2. In the caustic process NaOH is regenerated. Leaching occurs as per the reactions
above. The hot solution is allowed to cool (heat is recovered by heat exchangers for
preheating feed to leaching) and Al(OH)3 precipitates from solution. (Prior purification
processes are needed as well, especially to remove silica, i.e. SiO2, dissolved from
clay minerals. However, the problematic step of iron removal is avoided.) This is just
the reverse of reaction (13). This then regenerates the leaching reagent, which is
absolutely essential due to its high cost.

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In the acid process we could regenerate the acid as well. However, this poses
greater difficulties. Due to the very high affinity of Al(III) for oxygen-containing
ligands, the salt precipitated from HCl solution is [Al(H2O)6]Cl3. The final product of
the process needs to be Al2O3, which is suitable as a feed to molten salt electrolysis
to form Al metal at ~1000°C. At these temperatures, water must obviously be absent.
In the Bayer process, Al(OH)3 is calcined:

2Al(OH)3 s = Al2O3 s + 3H2O g ∆H° = 186 kJ/mol (19)

Calcination of [Al(H2O)6]Cl3 would require a lot more energy, since additional water
would have to be driven off, as well as HCl:

2[Al(H2O)6]Cl3 = Al2O3 s + 6HCl g + 9H2O g ∆H° = 959 kJ/mol (20)

Again, HCl can be recovered and reused, as with NaOH, but the higher energy costs
and issues around iron removal from the leach solution are prohibitively expensive.
The situation is worse for sulfate medium. Again a hydrated salt is formed,
Al2(SO4)3·nH2O (n = 6 or ~18, depending on conditions). In addition to driving off
water, H2SO4 g must be driven off in order to form Al2O3 again. Since sulfuric acid
boils at ~340°C, the energy involved in forming H2SO4 g is much higher than forming
HCl g; pure HCl is a gas at room temperature and pressure.

3. In principle an acid leach solution can be neutralized with base to precipitate

Al(OH)3. However, now all the acid is lost and base is consumed as well. This becomes
very costly. In addition, at ordinary temperatures a gelatinous Al(OH)3·nH2O
precipitate is formed that is almost impossible to filter.

4. In the acid leaching and calcination systems strongly acidic solutions and vapours
must be handled. These are much more corrosive toward steel than NaOH solutions.
In fact, mild steel may be used in many parts of the Bayer process.

In summary, this is a case where the chemistry and conditions downstream

from leaching determine the choice of leaching medium. This is a rare example of a
situation where a base metal is produced using a basic solution.

2.3 Characteristics of an Ideal Leaching Process

When we are trying to leach a mineral of interest the following features are
essential:

• The mineral must be soluble in an economically affordable solution.

• The metal must be economically recoverable from solution.

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• Co-extracted impurities must be capable of further separation.

• Gangue minerals should not consume excessive amounts of reagents.

• Solid-liquid separation must be feasible.

The following features are desirable:

• The leaching reagents should be recoverable or able to be regenerated for

recycling.

• The feed material should be free of clay minerals (clays often make separation
of the leach solution from the residual solids difficult).

• The feed material should be porous to allow good contact between the leach
solution and the desired minerals, providing a high surface area for reaction,
and lessening the extent of size reduction needed for the feed material.

• The leach solution should not be corrosive to plant equipment and materials.

• The leach solution should be as non-toxic as possible.

2.4 Summary of Common Leaching Processes

Based on the preceding section, it should come as no surprise that there is not
a great variety of leaching systems in practice. Some of the common processes are
summarized in the table below. Note the preponderance of sulfuric acid leaching
solutions (sulfate media). Some terms are explained here. Oxidized sulfides result
oxides, hydroxides, carbonates, sulfates, silicates, etc. Zinc calcine is the product of
roast ZnS, i.e. ZnO. A laterite is a weathered, near surface deposit. It has been in
contact with surface water (and hence some O2 as well) for an extended time. Nickel
laterites contain modest concentrations of nickel and roughly 1/10 as much cobalt.
Laterites contain oxides, hydroxides and aluminosilicates. A reduced laterite (nickel-
bearing) has been subjected to a reducing roast (e.g. by incomplete combustion of
hydrocarbon) prior to leaching. Oxidized gold ore is an original sulfide ore that has
undergone oxidation, e.g. naturally over geologic time. A refractory gold ore refers
to a sulfide ore that contains finely disseminated gold, or has other factors that
mitigate direct cyanidation. Scheelite, i.e. CaWO4, leaching by Na2CO3 is an example
of metathesis (exchange). CaCO3 is less soluble than CaWO4, so that soluble Na2WO4
goes into solution. Technically it is leaching with base, but metathesis per se does
not fit within the categories outlined in Figure 1.

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3. Overview of Types of Leaching Methods

There are many different types or categories of leaching. Figure 8 below

provides a comparison of some of the common types. The boxes in the figure indicate
specific types of steps involved in the process. Obviously complexity and costs
increase with the number of discrete steps involved. The value contained in the ore
based on the minerals present (actually, the fraction thereof that can be extracted!)
must be high enough to justify the effort and cost to be expended. From an economic
point of view, it is the $/tonne value of the ore that must be

Table 1. Summary of common leaching processes.

Solutio Oxidan Equipment/Metho
Feed Temp. Pressure
n t d
Oxidized Cu ore Dil. Ambien Atmospheri
None Heaps
(oxides etc.) H2SO4 t c
Dil. Ferric, Ambien Atmospheri
Sulfide Cu ore Heaps
H2SO4 bacteria t c
Cu,Ni,Co,Zn
Dil. Ferric, ~100 or
concentrates/matte 1-10 bar Tanks, autoclaves
H2SO4 oxygen >150°C
s
Dil. 40- Atmospheri
Zinc calcine (ZnO) None Tanks
H2SO4 90°C c
Ferric, Atmospheri
Ni matte Dil. HCl <100°C Tanks
cupric c
Dil.
Ni laterite ore None ~250°C ~50 bar Autoclaves
H2SO4
Air, 40- Atmospheri
Reduced laterite ore NH3/CO2 Tanks
Cupric 80°C c
Dil. Ferric + 40- Atmospheri
Uranium ore Tanks, in-situ
H2SO4 MnO2 50°C c
Ambien Atmospheri
Oxidized gold ore NaCN Air Heaps, tanks
t c
1 150-
1 H2SO4, 1 Ferric, 1 30-40 1 Autoclaves,
200°C,
Refractory gold ore, then: then: bar, then then
then:
concentrates
2 2
2 NaCN 2 air 2 tanks
ambient atmospheric
Bauxite i.e. 150-
NaOH None 20-40 bar Autoclaves
Al(O)OH 200°C
Roasted vanadium 50- Atmospheri
Water None Tanks, columns
ore 90°C c
Soda
Scheelite,
ash None 200°C 40 bar Autoclaves
i.e. CaWO4
(Na2CO3)

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considered. A gold ore containing only 10 g Au/tonne of ore (10 ppm) might be worth
running the most involved kind of process. A copper ore containing 0.5% Cu (5000
ppm) may warrant no more cost and effort than a heap leach.

Note that when we specify an ore grade (lie 0.5% Cu), we mean 0.5% by
weight, that is 5000 g Cu/tonne of ore or 5 kg/tonne. What this does not specify is
the mineral form in which the Cu resides. This causes no end of confusion. To clarify:

0.5% Cu as CuFeS2 (chalcopyrite) means 5 kg Cu/t ore in the form of CuFeS2,

i.e.

5000 g Cu 1 mol Cu 1 mol CuFeS2 185.513 g CuFeS 2 14,439 g CuFeS 2

× × × =
t ore 63.546 g Cu 1 mol Cu mol CuFeS 2 t ore

= 1.44% CuFeS2 [3]

Recall that crushing and grinding are stages of size reduction for an ore; first
it is crushed, and then ground where applicable. Lixiviant is an archaic term for
leaching solution, and it is still commonly in use.

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Increasing complexity and cost

Ore
Lix.

Dumps Crush Crush Crush Crush

Lix. Lix.

Heaps Vat Grind Grind

Lix.

Tank Pretreat

Lix.

Tank,
A/C

Months Days Minutes to hours

Years
to Years

Increasing value

Lix. = lixiviant = leaching medium

Figure 8. Classes of leaching processes showing common broad types of steps.
Source: University of Capetown, hydrometallurgy course notes.

3.1 In Situ Leaching

In situ is Latin for "in position." In terms of ore handling, this is the simplest
of all leaching methods (not indicated in Figure 8). The ore is not actually mined.

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Rather, a leach solution is pumped down into a rock formation (e.g. sandstone) at
various points and then solution is pumped back up to the surface at others. If the
ore body is not sufficiently porous, blasting may be used to rubblize it first.

This method of mineral extraction has long been used to recover soluble salt
deposits deep under ground. These are termed evaporate deposits. Application to
other minerals requiring more aggressive chemicals is more recent. This method has
been used for uranium and copper production. On the one hand, it is quite simple
since the ore rock is not removed from the ground. What is complicated about in situ
leaching is the solution flow through the ore and the presence of natural aquifers. If
leach solutions mix with an aquifer and flow out from the area, that water will be
contaminated with toxic chemicals. While metal values would be lost, the former
concern is by far the greater. A thorough knowledge of the hydrology of the area is,
therefore, essential. In illustration of an in situ leach system for uranium is illustrated
in Figure 9.

Monitoring Production
Injection
Injection well well well
well

Subsoil

Impermeable clay

Casing
Upper aquifer

Impermeable clay

Uranium-bearing
formation

Screen
Impermeable clay

Figure 9. Schematic illustration of uranium mining by in situ leaching.

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In situ leaching is applicable to quite low grade ores. It may be called bore
hole solution mining when applied to a new ore, and stope leaching when applied to
a previously worked out ore. In the case of the latter, this might involve tailings from
previous processing, dumped into an old pit or underground excavation. While the
process appears to be attractive in that ore handling is avoided, thus lowering capital
and some operating costs, metal extractions tend to be low and rates of extraction
are quite slow. At the Miami mine in Arizona copper was leached out of low grade
deposits left after ordinary mining ceased in 1954. Note that atmospheric oxygen is
unavailable due to the very nature of the leaching method. Thus if oxidation is
required for leaching, a solution reagent must be supplied. This may be prohibitively
expensive. A common form of uranium in nature is a non-stoichiommetric oxide,
UO2.x (x < 0.67). This requires an oxidant to be dissolved, forming [UO2]+2, which is
inevitably complexed with an oxygen-containing ligand, such as SO42-, CO32-, etc.
Where in situ leaching is used, H2O2 is added with the leach solution pumped into the
ground. The high value of uranium justifies the costly reagent. Leach solutions are
pumped up from a well, processed for metal recovery and the barren leach solution
is made up to suitable concentration of reagents again, and redirected back into the
formation. Note the presence of monitoring wells for the purpose of ensuring that
leached uranium is not getting into the upper aquifer. Sandstone formations bearing
uranium in the U.S. are an example of where in situ leaching may be practiced.

3.2 Dump and Heap Leaching

These methods are similar in that ore is mined and removed from the mine,
then piled up and treated with leach solution from the top. Solution works its way
down through the material and dissolves the minerals of interest and some gangue
minerals. Solution is collected from the bottom and processed for metal recovery.
Dump leaching is rather cruder, though, than heap leaching, as the word implies.
Dump leaching is applied to rejected ore, e.g. from an open pit mine, that has a grade
that is too low for the main process in use and to oversize ore from the mine that
cannot be crushed. Thus dump leach ore rock may exceed 1 m in size. Dump leaching
is a way to economically extract some value from what is otherwise waste material.
Dumps are located on natural slopes and leach solutions flow to a natural
drainage basin. There is minimal or no site preparation. Dumps may contain millions
of tones of ore, cover up to hundreds hectares and may be >100 m deep. A schematic
illustration of a copper dump leach is shown in Figure 10. Recoveries are modest,
typically about 60%.

Heap leaching has been in use for more than 500 years. An early citation
(1557) refers to a heap leach operation where alum, i.e. Al2(SO4)3·18H2O, was
recovered for use in the textile industry (cloth dying). Much more care and effort
goes into a heap leach than a dump leach. Optimizing economic extraction is a key
goal. Heap leaching may use mined ore without further size reduction (run of mine
ore; ROM), but often it is first crushed to some prescribed size range. These days,

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heap leaching is commonly practiced for gold, copper and uranium extraction.
Research is going on in order to extend it to nickel, zinc, etc.

Heap leaching, in contrast to dump leaching, uses a carefully constructed base

or pad. Ideally, the site is graded to a slope of about 1%. A heavy duty plastic liner
is placed on the base and ore is piled onto this. The slope drains towards a
collection trough along the edge of the heap to collect PLS. Again solution is applied

Figure 10. Schematic illustration of a copper ore dump leach. The dump may be built
up in layers as indicated. The impervious base is usually natural. Source: A.K. Biswas
and W.G. Davenport, Extractive Metallurgy of Copper, 2nd Edn., 1980, p. 264.

to the top of the heap, which is leveled. A number of methods may be used. Large-
scale sprinklers are used, as well as drip emitters. The latter involves a network
(usually on a 1 x 1 m grid spacing) of tubing where solution drips directly onto the
heap surface. These are good for minimizing water loss by evaporation and misting.
A pond for storage and surge capacity is built downstream of the collection ditch. PLS
is processed for metal recovery and the barren solution is then redirected back to
leaching. Make-up reagents are added as needed. A schematic illustration is shown
in Figure 11. A heap leach may pad may be kilometers long, hundreds of meters wide
and >100 m high. It will contain millions of tones of ore, mined at a rate of 10,000-
500,000 tonnes/day. The time frame for heap leaching a given ore runs from weeks
to years. Typical extraction efficiencies are moderately good; about 80%.

Copper heap leaching has been practice since about 1700. Gold heap leaching
began around 1969. Most of the world's hydrometallurgical copper production is
obtained from heap leaching operations. The biggest facility in the world is in Chile
and produced 145,000 tonnes of copper in 2010. A gold leach with as little as 0.5 g
Au/t ore (0.5 ppm!) can be profitable. Even some high grade gold ores with about 15

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g Au/t ore are being successfully heap leached. Roughly 12% of the world's annual
gold production comes through heap leaching. An average gold heap leach operation
produces about 5 tonnes Au/year (about 160,000 oz).

For gold extraction, heap leaching is often compared to agitated tank leaching.
The latter requires finely ground ore and energy-intensive agitation to

Reagents

Metal
recovery

Heap

Figure 11. Schematic illustration of a heap leach operation.

suspend ore particles and provide efficient contact with the leaching solution, in large
tanks. All of this adds considerably to capital and operating costs for extraction. Heap
leaching economics are often more favourable.

There are a number of important factors in the design of a heap leach.

Extensive laboratory testing, including using columns of ore, are devised to determine
suitable parameters. Some of the main factors are discussed below.

Leaching Chemistry

Copper ores are typically heap leached when a concentrate cannot be made.
This may occur in the case of low-grade Cu ores (e.g. <0.5% Cu) or when other
factors preclude making a concentrate, for example, oxidized ores cannot be easily
concentrated. Oxidized copper minerals (like CuO, CuSiO3·nH2O, Cu2CO3(OH)2, etc.,
are readily leached in dilute sulfuric acid. Gold/silver ores are leached with dilute
cyanide solutions and also require oxygen. The oxygen solubility in water from air is
often sufficient for this purpose.

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A sulfide ore containing minerals such as CuS, Cu2S and Cu5FeS4 requires
oxidizing conditions as well as sulfuric acid. Bacteria are generally used (thiobacillus
thiooxidans, etc.) and the leach also requires oxygen. The sulfide portions of the
minerals are ultimately oxidized to sulfate, solubilizing the metal ions. However, the
higher concentrations of minerals of interest means that oxygen from solution added
to the top of the heap will be depleted well before the bottom of the heap is reached.
Provision for blowing air up through the heap is then needed. Note that chalcopyrite,
CuFeS2, is not readily amenable to heap leaching. This mineral passivates soon after
leaching begins, possibly due to the formation of an

impervious and unreactive intermediate sulfide layer. Recoveries of copper from

bioleaching, or conventional ferric ion leaching are poor. If at all possible, chalcopyrite
and other copper sulfide minerals are concentrated and then smelted. Other sulfide
minerals may also be dissolved to some extent. Pyrite, FeS2, will be readily oxidized
by the bacteria. This may result in net acid production, whereas many other minerals
will consume acid. Where net acid is produced it may be necessary to implement
partial neutralization, which requires base and added expense.

Ore Size

An important issue in heap leaching is how finely the ore must be crushed in
order to obtain good extraction. Finely crushed ore may be more rapidly extracted
and perhaps to a higher degree, but this costs more. The enhanced extraction must
be sufficient to justify the extra cost. This ends up being a trade-off between
economics and technical possibility. In some cases the mined ore itself (run of mine
ore; ROM) is leached directly without size reduction. In other cases the ore is crushed,
even to the extent of using secondary cone crushers. If much fine material is
generated by size reduction, or if the ore contains a lot of clay minerals,
agglomeration may be needed. Otherwise the fine material may plug the heap and
render it impervious to solution flow. Often this involves rolling the ore inside a large
drum, with suitable reagents that bind the small particles. For gold ores this may
involve small additions of cement. For copper ores strong sulfuric acid solutions are
often used, particularly with oxidized ores. This acts to cause small particles to stick
together through modification of silicate mineral bonds. This has the double effect of
combining fine particles into porous agglomerates and jump-starting the leaching
process. Alternatively, clay minerals can be separated out by screening. The physical
nature of the ore has many important implications for heap leaching.

Heap Permeability and Solution Flow

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This is a complicated business and complex models have been developed for
understanding and predicting solution flow through heaps. Lab testing is needed to
determine how deep a heap can be. Efforts are made to maximize heap leach heights
in order to minimize the operation’s footprint and effects on the environment. Heaps
may be built in single layers (each layer is called a “lift”) or in multiple layers. Lifts
may vary in depth, but on the order of 10 m is typical. Heaps with multiple lifts may
reach heights in excess of 100 m. Here again the nature of the ore becomes very
important. Compaction of lower lifts may impede solution flow. Also, with increasing
height, it takes longer for fresh PLS solution from the upper lift to exit the heap at
the base. A photo of a copper heap leach with four lifts is shown below (Figure 12).

Figure 12. A copper heap leach in Northern Chile (elevation 3400 m). Note the
successive lifts (4 visible here). Source: R. Thiel, M.E. Smith, "State of the practice
review of heap leach pad design issues."

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Figure 13. A conveyor stacking system in operation. Source: Terra nova

technologies.

Stacking Procedures

There are two broad classes of ore stacking on heaps: truck stacking and
conveyor stacking. The physical characteristics of the ore and the rate of stacking are
important considerations. For a number of reasons smaller operations (10,000-
50,000 tonnes of ore per day) may more economically use conveyors. For ~100,000
t/d truck stacking is often preferred. For very large operations, stackers mounted on
caterpillar tracks are used. A photo of conveyor stacking equipment is shown in Figure
13.

3.3 Percolation Leaching

This is also known as vat leaching. A relatively low grade ore is crushed to
about 5-20 cm particle size and loaded into large tanks. Fine material is removed, or
possibly treated to agglomerate it. (As in heap leaching, fine material will plug the
tank bottom and also slow down solution flow through the ore mass.) The bottom of
the vat is often designed to be permeable to solutions. The vats are, in effect, very

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large filters. They are usually made of concrete and line with lead or wood. Capacities
may be up to 104 m3, with a bed depth of up to 6 m. The largest vats contained up
to 12,000 tonnes of ore. Vats are filled and emptied mechanically, which involves
high labour costs; the technology is prohibitively expensive in the developed world.

A series of vats may be used with solution flowing in essentially counter-

current fashion. This is illustrated in Figure 14. Fresh (and the most aggressive) leach
solution first contacts the most leached ore, which obviously still contains the
minerals that are hardest to leach. This affords the greatest driving force to most
fully leach the ore. On the other hand, the freshest ore contacts the most depleted
leach solution. However, the minerals that are easy to leach react easily with the
remaining leaching reagents. This ensures that reagents are well utilized. For
instance, if it is acid being used to leach an oxidized copper ore, then the weaker
solution contacting the fresh ore has a better chance to be used up. This is
economically favourable, especially when excess reagents have to be removed prior
to metal recovery steps.

Figure 15 shows details of what a percolation tank looks like. Solution may be
passed down through the ore or up. Upflow has the advantage of immersing the ore
charge in leach solution, allowing for better contact between ore and solution and
more efficient leaching. It may also minimize plugging of the bottom of vats.
However, upflow of solution precluded use of air as an oxidant, so the technique was
limited to oxide copper ores. While ore in some vats is being actively leached, other
vats may be emptied of spent ore, and other vats loaded with fresh ore. While
counter-current operation provided for high extraction efficiency (up to about 90%),
vat leaching has been largely displaced by heap leaching, which is easier to operate,
much more economic and suited to much larger scale.

Fresh ore Partially Spent ore

leached ore
PLS

Vat being Fresh Leached

loaded with leach ore being
fresh ore solution removed
Figure 14. Schematic illustration of percolation leaching using the counter-current
flow principle. Additional vats may be readied for leaching by addition of fresh ore
and tailings are removed from a fully leached vat.

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Figure 15. Schematic illustration of a leach vat. Floor areas were about 1700 m2.
Source: unknown.

3.4 Agitation Leaching

There are numerous types of agitated leaching systems. The common thread
is that ore is ground to small particle size (commonly on the order of 10-200 µm) and
suspended in a leach solution. Extensive size reduction adds to costs, but is necessary
to be able to achieve suspension. Both suspension in the slurry and high particle
surface area are necessary so that reactions are fairly rapid (minutes to hours). The
vessels and associated infrastructure are expensive and so maximizing reaction rate
minimizes required residence time, and hence equipment size and cost.
Understandably then, agitation in leaching involves an increase in capital and
operating costs. This is justified under various conditions: when the ore has high
value (moderate to high grade); metal values are finely disseminated in the ore and
fine grinding is required to effect mineral exposure. Other forms of leaching then are
not applicable since the ore is too fine now. Reactors may be operated in batch mode
or continuously. Continuous operation is more efficient. Examples of four types of
vessels are outlined in Figure 16.

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Figure 16. Types of vessels used in agitation leaching. (a) Pachuca tank, (b) low
speed agitation, (c) high speed agitation, and (d) pressurized, agitated autoclave.
Source: unknown.

Pachuca Tanks

These are named after a small mining town in Mexico where they were first
used. Pressurized air is blown up through slurry in a tall tank. The upward motion
causes slurry to be drawn up. A circulation pattern results as shown in the figure. A
central air lift tube may or may not be present. Reactors may be operated in batch
mode or slurry may be fed in continuously. Where oxygen is consumed agitation also
provides for dissolution of air in the solution. The air line may also come in from the
top and discharge near the bottom. Live steam (steam directly in contact with the
slurry) introduced with the air may be used to heat the slurry up to 70°C without
difficulty. Tanks are typically 3.5 m across, 14 m high and have a 60° conical bottom.
They may be made of wood, steel or rubber-lined steel. These reactors operate at
close to ambient pressure. Several reactors in series may be required to achieve the
required total residence time. They are used for acid leaching of oxide minerals and

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for cyanide leaching of gold. One problem with these is re-suspending the solids after
a power failure or shutdown. It is an old technology which is falling out of favour.

Low-Speed Agitated Leaching

These are used when high turbulence is not required. These provide off-bottom
suspension. Large diameter rakes or paddles may be used. This is suitable when the
reactions involved are relatively slow and not improved by intense mixing.

High-Speed Agitated Leaching

These are used when the chemical processes are fast and limited only by
diffusion of reagents to the mineral surface. (Upon contact the reactions occur; they
are fast.) Very good mixing is required to constantly replenish the reactants at the
mineral surface. Otherwise the reaction would be slowed by having to wait for
reactants to diffuse through solution toward the mineral surface. The agitator is
designed to pump slurry around rapidly. High power impellers are used. Depending
on the application, varying levels of shear may be required. The shape of the impeller
or turbine is quite important. Impellers designed for shear and flow are discussed
later in these notes. An example of where shear is needed is when air or oxygen has
to be introduced. Shear breaks up the gas flow into fine bubbles that have high
surface area and that are more rapidly absorbed by the leach solution. Baffled tanks
are employed to prevent the slurry from simply spinning around (vortexing) with
diminished efficiency of mixing. (This is treated in a bit more detail in the section on
agitation.) This type of leaching is often required when redox reactions are employed
(such as oxidation of sulfide minerals). Atmospheric pressure tanks are suitable for
temperatures below 100°C. Bacterial leaching of copper sulfide concentrates is an
example of where an agitated tank leach is used.

Agitated Autoclaves

When temperatures in excess of 100°C are required to obtain suitable reaction

rates, pressurized autoclaves are needed. Temperatures of up to 300°C are required
in some instances. Steam pressure at 300°C is 85 atm. Autoclaves are suitable for
concentrated feeds. They are expensive and costly to run, so the metal values in the
feed must be high to justify their use. Leaching times are typically short (10 min - 2
h).

Autoclaves are long and tube-shaped (like submarines). They may be

horizontally or vertically oriented. Vertical orientation allows for more autoclaves in
a given area. Often they are divided into a number of compartments. In a horizontal
autoclave (Figure 17) slurry flows in from one end and over weirs from one

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compartment to the next. Each has its own stirrer. Good agitation is essential

Figure 17. Schematic illustration of a horizontal, brick-lined autoclave vessel for

leaching of a metal sulfide concentrate. Source: R. Berezowsky et al, Journal of
Metals, 1991, pp. 9-15.

to suspend the solids, which promotes good leaching kinetics. (Minimizing residence
time in these expensive vessels is imperative.) Leached slurry is discharged from the
end of a horizontal autoclave via a pipe dipping below the surface. Modern autoclaves
are operated by continuous charging and discharging, and not in batch mode. Vertical
autoclaves are commonly used in the alumina industry (Bayer process) and
sometimes in processing of nickel laterite ores.

Horizontal autoclaves are filled to 65-70% of their volume. Reagents may be

injected into each compartment. Oxygen gas is injected for oxidation of sulfides. The
extent of oxidation of the sulfide depends on the relative amounts of O2 and mineral
sulfide. Due to reagent consumption costs, it is preferable to leach sulfides to
elemental sulfur (1/2 mole O2 per mole of S2-) rather than sulfate (2 mole O2 per
mole S2-). Oxygen from air is readily concentrated, e.g. by a cryogenic process to
99%. A horizontal autoclave is needed if oxygen is to be used. Inert gas impurities
(like N2 in the O2 or CO2 generated from reaction of acid with carbonate minerals) is
continually vented. This maintains a high partial pressure of O2. Where sulfide

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minerals are involved, oxidation by O2 liberates heat. Some of this heat may be
recovered to preheat the incoming feed slurry. If the sulfide content of the solids is
high enough, the process will be energetically self-sustaining (autogenous). This is
certainly desirable from an economic standpoint.

Autoclaves must be designed to withstand high pressures and temperatures.

They also contain harsh chemical environments, which promote corrosion of steel.
In caustic systems (Bayer process) mild steel may be used, largely because of a
protective scale that forms. Some Ni/Co sulfide concentrates are leached using
oxygen in an ammoniacal medium, i.e. NH3/(NH4)2SO4. In this case the autoclave
may be made of stainless steel, or have stainless steel cladding. For acid systems
(H2SO4 medium in particular) the autoclave will can be carbon steel, but lined with
brick and lead. Titanium has been used because of its high strength and good
corrosion resistance in acid solutions, so long as an oxidizing condition is maintained.
Titanium is also more resistant to corrosion by chlorides than is steel. The TiO2 scale
that forms on titanium is very strong and adherent, protecting the underlying metal
from corrosion. However, titanium itself is strongly reducing and fresh titanium metal
surface exposed to high pressure oxygen will combust, causing an extremely hot fire.
Erosion is another possible means by which fresh titanium metal may be exposed.
The use of titanium autoclaves requires great care.

Some important examples of autoclave leaching are given below:

• The Bayer process mentioned previously uses autoclaves for leaching.

• Nickel laterite ore leaching, particularly in Cuba. The ore is comprised of

oxides and hydroxides, especially of iron, as well as aluminosilicates. Strong
sulfuric acid at high pressures and temperatures is used to leach nickel and
cobalt into solution. Oxygen is not needed for these reactions. The nickel
and cobalt are then precipitated with H2S to form a synthetic concentrate of
NiS and CoS.

• The NiS/CoS concentrate from Cuba mentioned above is shipped to Fort

Saskatchewan, Alberta to be leached and then converted into pure nickel
and cobalt. The leaching process uses ammonia/ammonium sulfate and
oxygen gas as oxidant. After purification [Ni(NH3)6]+2 and then [Co(NH3)6]+3
in solution are reduced to the metals using hydrogen gas, again in
autoclaves.

• Sphalerite concentrate (ZnS) is leached using autoclaves at about 150°C

and oxygen gas. The mineral is oxidized in sulfuric acid to form aqueous
ZnSO4 and elemental sulfur. Oxygen is the oxidant.

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• Gold is sometimes very finely disseminated in pyrite, i.e. FeS2. Grinding

does not liberate the gold particles and thus leaching of ground pyrite
concentrate with cyanide directly may be unsuccessful. In such cases the
pyrite may be first oxidatively destroyed in an autoclave using acid and
oxygen. The residue can then be leached with cyanide to extract the gold.
Since a concentrate of pyrite is made, the gold value in the pyrite may be
quite a bit higher than in the ore as a whole. This may justify the added cost
of autoclave processing.

3.5 Co-Current and Counter-Current Leaching Methods

In continuous leaching there are two basic configurations: co-current leaching

and counter-current leaching. Counter-current leaching was already mentioned
briefly in the context of vat or percolation leaching. The important thing to bear in
mind is that we have two streams - a solid stream of material being leached, and a
solution stream doing the leaching. These streams may flow in the same direction,
or in opposite directions. When the solids and solution flow in the same direction it is
co-current leaching. When they flow in opposite directions it is counter-current
leaching. A schematic illustration of the two types is shown in Figure 18. Making the
solids and solution flow in the same direction is easy enough. Usually there is a solid-
liquid separation after the final leach step. This is indicated in part (a) of Figure 18.
Moving the solids and solution in opposite directions is a bit more challenging. The
way that this is accomplished is by having a solid-liquid

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Department of Materials Engineering Introduction to Leaching

(a) Concentrated
leach solution
Partially Well
leached leached
Ground slurry slurry L
1 2 3 PLS
ore + S
water

Tailings

(b)
Substantially depleted reagents/
Partially depleted reagents/
higher [Metal ions]
moderate [Metal ions]

S L L
1 2 S 3 S
L
Ground
ore + Partially
PLS: More- Tailings
water leached
depleted leached Concentrated
solids Well-
reagent / solids leach solution
highest leached
[metal] solids

Figure 18. Schematic illustrations of (a) co-current, and (b) counter-current leaching.
Note the net flow of solution from right to left and flow of solids from left to right in
part (b).

separation after each leaching stage. Fresh leach solution enters from one end and
PLS leaves at the other (right to left in the diagram (b) above); solids enter from the
other end and flow against the direction of the solutions (left to right in diagram (b)
above). The basic differences noted here are sufficient to distinguish co-current and
counter-current leaching processes.

The advantages of co-current leaching are simplicity and lower capital and
operating costs. The disadvantages may sometimes be either loss of valuable
minerals, or excessive use of reagents and associated costs of coping with high left
over reagent concentrations. Note that countercurrent processing need not always
present this trade-off, but sometimes it does. The advantages of counter-current

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Faculty of Applied Sciences Course Notes – Chapter IV:
Department of Materials Engineering Introduction to Leaching

leaching may be both higher extents of leaching of valuable and more efficient use
of reagents. The disadvantages of counter-current leaching are a more complex and
expensive leaching process (both capital and operating costs). And, finally, the
minerals being leached or the nature of the leaching process may not always allow
for a counter-current option, e.g. high-pressure auotclaves.

Obviously the counter-current system is more complex and has more

equipment; thus it is more expensive. There has to be a good reason to go to employ
this extra complexity and cost. If recovery of valuable metal can be substantially
enhanced and reagent costs substantially lowered, compared with co-current
leaching, then counter-current leaching may be worthwhile.

One instance where counter-current leaching may be pursued is when metal

values are contained in more than one mineral, at least one of which requires
aggressive conditions to leach. This is best illustrated with an example. The main zinc
mineral in nature is sphalerite, ZnS. This is separated from ores as a concentrate.
However, concentrates are never pure and inevitably some pyrite and other minerals
report to the concentrate. Sphalerite concentrates are commonly roasted in air. The
product is called zinc calcine. This forms ZnO (the main constituent of roasted
sphalerite concentrate). However, in the process ZnS and FeS2 also form zinc ferrite,
ZnFe2O4. Zinc oxide is readily leached in dilute sulfuric acid:

ZnO s + H2SO4 aq = ZnSO4 aq + H2O l (21)

On the other hand, ZnFe2O4 requires stronger acid and higher temperatures in order
to leach. In the co-current leach system it would be necessary to have high
concentrations of acid in the latter stages of leaching in order to leach ZnFe2O4, after
the ZnO had been leached. (The ZnO-ZnSO4 mixture buffers the pH so that the low
pH needed to leach ZnFe2O4 cannot be attained until the ZnO is consumed.) Thus the
solution exiting leaching would have a high H2SO4 concentration. This would have to
be neutralized prior to solution purification and metal recovery, which would cost too
much. Hence in the earlier versions of the roast-leach-electrowin (RLE) process zinc
in ZnFe2O4 was not recovered.

Counter-current leaching offers a way to recover this zinc and avoid

excessively high acid concentrations in the final leach solution. This is illustrated with
the flowsheet in Figure 19, which shows how the leach process fits into the overall
process. As the calcine passes through leaching, the more easily leached minerals
(ZnO, in particular) dissolve first. The most resistant (or refractory) minerals persist
until the final stage of leaching. Further, the strongest acid and highest temperature
(the most aggressive conditions) are employed in this stage in order to leach ZnFe2O4.
This is often called the hot acid leach (or just the acid leach). After solid-liquid
separation the solids exit as tailings and the solution is directed back to the preceding
stage, still high in acid and somewhat enriched in ZnSO4. In the first stage the fresh
calcine enters the leach circuit. This readily dissolves even in quite dilute acid

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Faculty of Applied Sciences Course Notes – Chapter IV:
Department of Materials Engineering Introduction to Leaching

(typically pH ~4). This is called the neutral leach due to the weakly acidic pH. The
excess of strong acid concentration is thus substantially used up and much of the
ZnO dissolves. The highly enriched leach solution exits the each circuit after solid-
liquid separation to go on to purification and metal recovery (by electrowinning for
zinc), while the solids proceed on to further leaching.

This has two beneficial effects that work together. One is that zinc values
locked up in ZnFe2O4 are leached, and the main reagent (H2SO4) is efficiently used.
The former generate revenue; the second saves money. In RLE processes for zinc,
there are numerous variations on the counter-current leaching theme, and many are
economically viable.

Figure 19. A counter-current leaching flowsheet for zinc production by the RLE
process. Acid is generated in electrowinning and thus spent electrolyte is recycled
back to leaching. Some additional acid may be needed in leaching, as indicated by
the dashed line. Modified from source unknown.
Note: Zinc processing by the RLE process has the further complication that
iron must be removed from the leach solution, and this is typically done within the
leaching process (not shown in Figure 19). There are three basic ways to do this,
depending on the form of ferric ion to be precipitated. These are formation of:
Fe(O)OH (goethite), Fe2O3 (hematite) and MIFe3(SO4)2(OH)6 (jarosites; MI = M+1;
usually NH4+ or Na+). Jarosite precipitation has been traditionally a common method
for iron removal. The leach stages and jarosite precipitation may be integrated in

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Faculty of Applied Sciences Course Notes – Chapter IV:
Department of Materials Engineering Introduction to Leaching

numerous possible ways, and it is not uncommon to perform jarosite precipitation on

the solution after hot acid leaching and before directing it back into neutral leaching.
In all this additional complexity, one can often discern an underlying counter-current
leaching process, despite intermediate processing of the leach solution between the
hot acid leach and the neutral leach.

An example of co-current leaching is next. Figure 20 is a flowsheet for a

bacterial leach process for pyrite (FeS2). The pyrite contains finely disseminated gold
(too fine to expose even by fine grinding). The pyrite from the ore is concentrated,
and thus removes most of the gold from the ore. The pyrite must then be destroyed,
which is accomplished by using thiobacilli bacteria to oxidize pyrite to ferric ion and
sulfate. This then leaves a solid residue that contains unleached gangue and the gold.
This is an instance where it is the solid residue that is desired rather than the solution;
the solution is simply neutralized as cheaply as possible (CaCO3) and disposed of.
The solid residue is directed to a cyanidation plant for gold recovery. Note the
presence of the cooling system. Oxidation of pyrite concentrate generates a lot of
heat. If excess heat is not removed the temperature in the leach tanks will rise to
>40°C and kill the bacteria. Note also that air is introduced into each tank to facilitate
oxidation of pyrite. Sulfate medium is ideal for this process since the bacteria are
oxidizing sulfur (formally S22- in FeS2) to sulfate and dilute sulfuric acid solutions are
not too severely corrosive.

Leaching occurs in a series of tanks and the solids and solution both flow in
the same direction. There is a single solid-liquid separation process at the end of
leaching. These two features are diagnostic of co-current leaching. In this case there
is no need for the more involved counter-current mode. There is one main mineral of
interest (pyrite). Gold is not locked up in other more resistant minerals, hence no
hard-to-leach minerals that might otherwise warrant counter-current operation. In
addition, the bacteria required a fairly narrow range of conditions. Hence increasingly
extreme conditions would be detrimental. Finally, the only real reagent used in the
leaching process is oxygen from air, which comes at a uniform concentration of about
21% O2. (Sulfuric acid is a product of the reaction.) Overall, then, counter-current
leaching is not really even feasible in this case.

3.6 Agitation

Principles

An agitator or mixer is a device that imparts energy to a fluid by means of a

rotated impeller. The hydraulic behaviour of an impeller is much like that of a

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Faculty of Applied Sciences Course Notes – Chapter IV:
Department of Materials Engineering Introduction to Leaching

Water Nutrients

Regrinding
circuit
Cooling
tower

Feed “Stock
tank”

Bacterial
leaching

Air S
Cyanidation
and gold L
recovery

Neutralization
(CaCO3),
disposal

Figure 20. Typical Biox flowsheet for bacterial leaching of pyrite in sulfuric acid
medium, using the co-current leaching method. (Note there are three tanks in which
leaching occurs in parallel; a three-tank first stage leach. This is followed by three
more tanks in series. Finally, there is one solid-liquid separation at the end of the
leach process. Source: Goldfields Ltd.

pump, with the difference that an impeller does not have a housing. The fluid may
be any mixture of liquids, solids or gas. The mixer provides two functions: flow and

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Faculty of Applied Sciences Course Notes – Chapter IV:
Department of Materials Engineering Introduction to Leaching

shear, in varying degrees. Flow is essentially pumping of fluid or slurry. Shear can be
thought of as a tearing of the fluid or slurry. It generates turbulence. Shear occurs
when a fluid passes through a significant velocity gradient. The fluid or

slurry then undergoes rapid change in velocity. This results in differential forces. This
is important for dispersing one phase in another, for instance. Shear greatly increases
the surface area of the dispersed phase. This is illustrated schematically below:

Figure 21. Illustration of how shear increases surface area of a dispersed phase.

Different impellers impart different degrees of both effects. A table of applications

and impeller types is provided below. The different impeller types are discussed
further on. Heat transfer and blending involve quite simple mixing. Solids suspension
is important for effecting good mass transfer of reagents to solids for leaching, for
instance. Solids suspension is probably the single most important agitation function
in hydrometallurgy. Gas-liquid dispersion is needed for getting low-solubility gases
into solution, again for example for leaching involving oxygen. Liquid-liquid dispersion
is required when a chemical species must be transferred from one immiscible phase
to another (e.g. in solvent extraction). Emulsification is not common in
hydrometallurgy. De-agglomeration is the breaking up of particle aggregates into its
constituent smaller particles by means of high shear.

Table 2. Some common mixing operations and the type of impellers required.

Application Impeller Type

Heat transfer Hydrofoils
FLOW Blending Propellers
Solids suspension Axial flow impellers
Gas-liquid dispersion Radial flow impellers
SHEAR
Liquid-liquid dispersion Flat blade turbines

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Faculty of Applied Sciences Course Notes – Chapter IV:
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Emulsification Disc turbines

De-agglomeration Homogenizers

The effectiveness of an impeller is limited by the viscosity of the fluid or slurry.

A maximum of ~500,000 cps (centipoises) is the limit for using an impeller. (Water
at 20°C has a viscosity of about 1 cps.) Agitators are comprised of:

(i) A power source (usually an electric motor).

(ii) A transmission (e.g. a gear box) to convert applied power into torque.
(iii) A shaft to transmit power from the motor to the impeller.
(iv) An impeller to transmit energy to the fluid.
(v) A seal system if the tank is closed and under pressure.

The power required to drive an impeller is given by the equation:

P = NPρN3D5 (Watts) [4]

where NP = a constant
ρ = fluid density (kg/m3)
N = rotation rate (sec-1)
D = impeller diameter (m)

(The actual power required is greater than that indicated by the equation due to
transfer inefficiencies.) When one considers the units, this is reasonable:

kg m-3 x sec-3 x m5 = kg m sec-2 m sec-1 = N m sec-1 = J sec-1 = Watts

The hydrodynamics of various impeller designs may be compared by means of a

dimensionless “power number,” NP,

P
NP = [5]
N D5 ρ
3

This is the ratio of applied power to the actual effect. It varies from one impeller to
the next, i.e. it's a characteristic of the impeller. It is a friction factor or drag
coefficient. The larger NP is, the harder it is to turn the impeller; a measure of friction
loss. Naturally the power number for an impeller depends on its shape, but, it also
depends on the Reynolds number. (Recall that the Reynold's number, Re, relates
inertial force and viscous force; it is the ratio thereof. Hence, as we would expect,
the viscosity of the fluid plays an important role in the power number.) For fully
turbulent flow the power number for a given fluid is roughly constant. And, turbulent
flow is what is needed for good mixing in hydrometallurgical applications.

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Faculty of Applied Sciences Course Notes – Chapter IV:
Department of Materials Engineering Introduction to Leaching

Low shear/high flow impellers have lower NP than high shear impellers. An
efficient hydrofoil may draw 1/20 of the power of a radial turbine (see below for
impeller types). However, the power number may also affected by viscosity and
clearance between the tank bottom and the impeller. Under fully turbulent conditions
(which is desirable for good mixing) the power number does not change with flow
velocity. Clearance from the bottom of the tank to the impeller is an important
variable. For efficient hydrofoils the clearance is normally equal to one impeller
diameter. Decreasing clearance impedes fluid flow and increases the power number.
This is a complex subject and will not be treated in detail here. Engineering of mixing
systems is an important task in hydrometallurgical processes.

Pumping capacity and shear can be compared for a given impeller and related
to the impeller diameter and its rotation speed. The relationships can be obtained
from dimensional analysis.

(i) As above,

P ∝ ρN3D5 [6]

Q = pumping capacity in units of m3 sec-1 (volume flow rate). Therefore,

Q ∝ ND3 [7]

(Volume pumped is directly related to the impeller diameter3. In fact,

Q = NqND3 [8]

where Nq is the constant of proportionality, and is called the flow number. As with
the power number, it is different for different impeller designs.) Let H = shear, also
called velocity head. It has units of energy/mass, which is reasonable for imparting
turbulence to a fluid:

J kg-1 = N m kg-1 = kg m2 sec-2 kg-1 = m2 sec-2, i.e. velocity2. Hence,

H ∝ N 2 D2 [9]

Then,

P ∝ ρN2D2·ND3 [10]

P ∝ ρHQ [11]

(ii) From:

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Faculty of Applied Sciences Course Notes – Chapter IV:
Department of Materials Engineering Introduction to Leaching

P = NPρN3D5 [12]

we obtain,

1/ 3
 P 
N =   D-5/3 [13]
 NP ρ 

For a given fluid, fixed power and a given impeller, P/NPρ is a constant. It follows
that,

N ∝ D-5/3 and D ∝ (1/N)3/5 [14]

From:

P ∝ ρHQ [15]

and for a given fluid (fixed ρ), and recalling that P ∝ N3D5 and Q ∝ ND3,

P N3D5
H∝ ∝ ∝ N2D2 [16]
Q ND3

Recalling that N ∝ D-5/3 then,

H ∝ (D-5/3)2D2 ∝ D-4/3 [17]

(iii) Q ∝ ND3 ∝ D-5/3D3 ∝ D4/3 [18]

(iv) Finally, the ratio Q/H may be calculated:

Q D 4/3
= -4/3 = D8/3 =
(1/N) ( )
3/5 4/3
( )
3/5 8 / 3
= (1/N) = (1/N)
8/5
[19]
H D (1/N)3/5 ( )− 4/3

Therefore, at constant power,

Q/H ∝ D8/3 ∝ 1/N8/5 [20]

What this means is that for a given fluid, power input and impeller, the ratio
of flow to shear for a particular impeller varies as impeller diameter8/3. In other words,

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Faculty of Applied Sciences Course Notes – Chapter IV:
Department of Materials Engineering Introduction to Leaching

flow increases by almost the cube of diameter. For a given power, increasing the
impeller diameter dramatically increases the flow effect relative to the shear effect.

Similarly, increasing the rotation speed (N) at constant power increases shear
relative to pumping capacity, though to a somewhat smaller extent (the exponent is
1.6). For high shear, small impellers run at high speed are most suitable. For high
flow, large impellers at low speeds are best. Intuitively this should stand to reason.
A low speed at the impeller tip should impart low shear. Obviously high shear and
high pumping capacity are conflicting objectives. Where both are needed a balance
of the effects must be struck.

The various parameters of concern for an impeller are N, D, P, Q, H, NP and

Nq. The two dimensionless numbers are characteristics of the impeller. The density
(ρ) is a characteristic of the fluid. In the preceding discussion we compared the effects
of N and D on flow and shear with other parameters held constant. There are also
many bases of comparison for different impellers, which are important considerations
for design. For instance, power required for a given flow and speed, or power required
for constant speed and diameter, or power required for constant flow and diameter,
etc. To illustrate, for a given fluid (constant ρ), impeller size (constant D) and flow
(Q = ND3 = constant, i.e. the desired flow effect is fixed or known) the power required
for two different impellers can be compared, As above,

P = NPρN3D5 [21]

Then for impellers 1 and 2 the power required for the two can be compared as follows:

P2 NP2 ρ(Q Nq2 ) D

3 -4 3
N  Nq1 
= = P2   [22]
P1 NP1ρ(Q Nq1 ) D
3 -4
NP1  Nq2




Impellers and Tanks

High shear occurs mainly in the vicinity of the impeller tip as indicated in the
diagram below (Figure 22). Hence it is important that all the fluid be directed to the
impeller blades. With blades attached to a central disk fluid is directed towards the
blades and is prevented form flowing axially past them.

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Faculty of Applied Sciences Course Notes – Chapter IV:
Department of Materials Engineering Introduction to Leaching

∆V/∆Y

Figure 22. Illustration of how a vertical, flat-blade turbine effects shear, particularly
at the tip of the impeller. The effect is greatest at the centre of the blades.

There are three general classes of impellers. These are illustrated in

Figure 23. Generally, axial-type impellers (hydrofoils and propellers) provide high
rates of pumping and low shear. Radial impellers produce lower pumping rates and
high shear. Normally the impeller is located along the vertical centre line axis of the
tank and pumps down. Then fluid flows up the sides of the tank. The ratio of impeller
diameter to tank diameter (D/T) is normally between 0.25 and 0.4. Low D/T ratios
are used for high horsepower, radial-flow impellers. An example is dispersion of two
immiscible liquids (as in solvent extraction). High D/T ratios are used for high
viscosity and high slurry pulp density (i.e. high % solids in slurries). Flow patterns
for radial and axial impellers are further illustrated in Figure 24.

Aspects of the tank are also important in design. An agitator operating in a

cylindrical tank with smooth sides will simply swirl the fluid around the tank with little
up and down circulation. In addition, a vortex is created in the middle with the effect
that the fluid is pushed up the sides of the tank. This simply converts kinetic energy
into gravitational potential energy and lowers mixing efficiency. To overcome this,
baffles are placed on the sides of the tank to induce a vertical circulation, as shown
in Figure 24. Normally four, equidistant baffles are used. For a cylindrical flat bottom
tank, which is common in hydrometallurgy, the ratio of the tank diameter to the fluid
depth is normally about 1.0. (An agitated autoclave chamber is not an upright
cylinder.) An illustration of a stirred tank reactor using a radial turbine impeller is
shown in Figure 25. This application is required when mixing gases (e.g. oxygen or
air) into a leach slurry.

Where there is to be an overflow of slurry the solids must be very well

suspended, which may require a larger agitator. Where tanks are arranged in series
and slurry overflows from one tank to the next, some of the solids will migrate across

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Faculty of Applied Sciences Course Notes – Chapter IV:
Department of Materials Engineering Introduction to Leaching

the top of the slurry and flow into the next tank, unless measures are taken to prevent
this. This greatly reduces residence time in the tank and therefore the extent of
leaching. The term for it is, "short circuiting." It can be overcome by using
downcomers. These are pipes that dip deep into the tank to deliver slurry from the
previous tank. Upcomers are used to draw off slurry from near the bottom of the
tank, rather than allowing it to simply overflow from the top. This acts to prevent
coarse, heavy solids from collecting at the bottom of the tank. Flow in the vicinity of
the upcomer is fast and draws up the large particles.

Agitation rate, Solids Suspension and Leaching Rate

Leaching involves a heterogeneous reaction between a solid and a solution.

(In leaching oxygen may also be used, but usually it reacts slowly with the solids,
and an intermediate oxidant (like Fe+3) is used as well; ferric oxidizes the minerals
of interest and oxygen oxidizes Fe+2 back to Fe+3. Since the leaching reaction is
heterogeneous the key is to get solution to the solids rapidly. For this to occur
efficiently the solids should be suspended. (If the solids lie in a heap at the bottom
of the tank, obviously it will take a lot longer for solution to make its way to the
particles.) Studies of agitated leaching often include an investigation of impeller
speed (rotation rate) and reaction rate. Reaction rate can be expressed in numerous
ways, but it is essentially the rate of consumption of a reactant, or the rate of
production of a product, i.e. change in concentration per unit time, or just change in
amount per unit time. The typical kind of plot obtained in such studies is shown in
Figure 26. At some threshold power level a small fraction of the solids

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Faculty of Applied Sciences Course Notes – Chapter IV:
Department of Materials Engineering Introduction to Leaching

Radial flow turbines

Np = 2.5-4.75
Nq = 0.95-1.23
Applications:
•High shear
•Gas-liquid dispersion
•Liquid-liquid (immiscible) dispersion
•Low level mixing

Pitched blade turbines

(Constant angle of attack)
Np = 0.9-1.62
Nq = 0.68-0.86
Applications:
•Moderate shear/moderate flow
•Moderate viscosity mixing
•Inexpensive for use as an axial flow
impeller
•High-intensity mixing for flow-
dependent applications

Pitched blade turbines

(Variable angle of attack)
Np = 0.3-0.6
Nq = 0.6-0.7
Applications:
•High flow/low shear
•Low to moderate viscosities
•Position relatively high off tank
bottom (compared with other impeller
types)

Figure 23. Basic impeller styles and flow patterns. Adapted from P. McGovern,
Hayward Gordon Ltd., "An introduction into fluid mixing and agitator design."

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 MTRL 358: Hydrometallurgy I
Faculty of Applied Sciences Course Notes – Chapter IV:
Department of Materials Engineering Introduction to Leaching

A typical axial flow pattern in

Some axial flow impellers a baffled, cylindrical tank.

A typical radial flow pattern

Some radial flow impellers. in a baffled, cylindrical tank.

Figure 24. Examples of impellers sold by Ligthnin (Rochester, New York), and flow
patterns in baffled tanks. Source: Lightnin and unknown.

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 MTRL 358: Hydrometallurgy I
Faculty of Applied Sciences Course Notes – Chapter IV:
Department of Materials Engineering Introduction to Leaching

(The figure is a side view with

four blades shown.)
Tank
Impeller diameter: Di = 1/3Dt
Impeller height from tank
bottom: Hi = Di

Impeller blade height:

q = 1/5Di

Impeller blade length:

r = 1/4Di

Blades Fraction of blade width

mounted on central disc
Disc = r/2 = 1/8 Di

Slurry or solution depth:

Hl = Dt
4 baffles from tank bottom to
above liquid surface

Baffle width: Wb = 1/10 Dt

Figure 25. A stirred tank reactor for gas dispersion and leaching using a 6-blade
vertical turbine. For other applications parameters may vary somewhat. Source:
unknown.

starts to become suspended. The extent of particle suspension increases as power

increases. Then the log of the reaction rate rises linearly with log(power), or with
log(rotation rate) (as is often presented instead). This continues until all the solids
have been suspended. This is called the off-bottom suspension point. Beyond this
point, further increases in applied power result in only modest gains in reaction rate.
What is occurring here is that the solids begin to become more uniformly distributed
throughout the slurry, and the increased turbulence does slightly improve mass
transport and hence reaction rate.

There are other considerations as well. For example, in bioleaching involving

stirred tanks air is added as the oxidant. Good dispersion of the gas requires an
impeller hat can impart shear. But, this means that the bacteria doing the leaching
also experience high forces that can physically destroy them. Hence a trade-off has
to be worked out. In gold leaching activated carbon is often added to the leaching
slurry. It is a very good adsorbent for [Au(CN)2]-. The larger carbon particles are then
recovered by screening to separate them from the ore solids, and the solution. If the

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 MTRL 358: Hydrometallurgy I
Faculty of Applied Sciences Course Notes – Chapter IV:
Department of Materials Engineering Introduction to Leaching

impeller tip speed is too fast, then the carbon particles get rapidly broken up, making
separation by screening impossible.

Off-bottom
suspension point

Figure 26. Typical trend in rate of leaching as a function of applied power to the
impeller. The rotation rate is often used as a proxy for power as well.

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